Inorganic modified composite gel material and preparation method thereof
By introducing carboxyl and amino grafting interfaces on the surface of Co3O4 and forming a synergistic network with the PAA framework, the problems of insufficient active site regulation, stability and recycling performance of Co3O4-based catalysts are solved, and efficient CO2 reduction and catalytic stability are achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHAANXI UNIV OF SCI & TECH
- Filing Date
- 2026-04-20
- Publication Date
- 2026-07-17
AI Technical Summary
Existing Co3O4-based CO2 reduction catalysts face challenges in regulating surface active sites, nanoparticle stability, catalyst recycling performance, and optimizing the gas-liquid-solid three-phase interface, resulting in insufficient catalytic activity and stability, making it difficult to achieve efficient enrichment and conversion of CO2.
Residual carboxyl groups were introduced onto the surface of Co3O4 by citric acid-assisted calcination. Molecular-level carboxyl-amino proximity interfaces were constructed by selective grafting with APTES, and a coordination-hydrogen bond synergistic network was formed using PAA as a gel framework. This optimized the electron density and proton transfer at Co sites, resulting in a highly efficient gas-liquid-solid three-phase interface.
It significantly improves the selectivity and reaction rate of CO2 reduction, achieves stable catalyst anchoring and efficient CO2 interface enrichment and conversion, and enhances the stability and recycling capacity of the catalyst.
Smart Images
Figure CN122399902A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of gel material synthesis technology, specifically relating to an inorganic modified composite gel material and its preparation method. Background Technology
[0002] With carbon emissions becoming increasingly prominent, CO2 capture and catalytic reduction have become important pathways to alleviate environmental pressure and achieve carbon resource recycling. Cobalt-based oxides (especially Co3O4) are widely used in the field of CO2 reduction catalysis due to their excellent electronic conductivity, abundant active sites, and good CO2 adsorption and activation capabilities.
[0003] However, existing Co3O4-based CO2 reduction catalysts still face many technical bottlenecks in practical applications: Firstly, the modification of active sites on the Co3O4 surface lacks precise control, and conventional preparation processes struggle to construct ordered functional group interfaces on its surface, making it difficult to regulate the electron density of Co sites. The imbalance in the adsorption intensity of CO intermediates restricts the kinetic efficiency of proton-coupled electron transfer (PCET), affecting catalytic activity and selectivity. Secondly, Co3O4 nanoparticles are prone to aggregation, and existing loading methods are insufficient to achieve their firm anchoring, leading to the loss of active sites and further reducing catalytic stability. Thirdly, the catalyst has poor regeneration performance and lacks a tunable reversible structure, making it difficult to recycle and reuse after use, increasing application costs. Fourthly, existing gel composite catalytic systems mostly adopt a single cross-linking method, which cannot simultaneously consider catalyst anchoring stability, proton transfer efficiency, and gas-liquid-solid three-phase interface optimization, making it difficult to achieve efficient enrichment and conversion of CO2.
[0004] To address the aforementioned technical challenges, developing a composite gel catalytic material capable of precisely regulating the microenvironment of Co3O4 active sites, achieving stable catalyst anchoring, and possessing both high catalytic performance and recyclability has become an urgent technical need in this field. Summary of the Invention
[0005] To overcome the shortcomings of the prior art, the present invention aims to provide an inorganic modified composite gel material and its preparation method. This method involves introducing residual carboxyl groups onto the surface of Co3O4 through citric acid-assisted calcination, guiding selective grafting of APTES, and constructing a molecular-level carboxyl-amino proximity interface. The carboxyl groups reduce the electron density at Co sites through electron-withdrawing effects, thereby weakening CO adsorption. The amino groups act as proton donors, shortening the proton transfer distance, thus synergistically optimizing the PCET kinetics of CO2 reduction and improving CO selectivity and reaction rate. Using PAA as the gel framework, the -COO... -A coordination-hydrogen bond synergistic network is constructed by coordinating and crosslinking with Co sites, and by using residual -COOH groups and amino groups for assisted crosslinking. This network enables stable anchoring of the catalyst and, through the carboxyl-amino acid base pair effect, establishes low-barrier proton channels, forming a highly efficient gas-liquid-solid three-phase interface, promoting CO2 interface enrichment and efficient conversion.
[0006] To achieve the above objectives, the present invention employs the following technical solution: This invention provides an inorganic modified composite gel material comprising the following parts by weight: 2 parts aminoCo3O4, 0.5-1.2 parts NH4HCO3, 3 parts glycerol, 9-15 parts acrylic acid, 9-15 parts potassium hydroxide, 0.5 parts MBAA (N,N'-methylenebisacrylamide), 0.5 parts ammonium persulfate, and 50 parts deionized water.
[0007] Further, the aminoCo3O4 comprises materials in the following mass ratio: cobalt nitrate hexahydrate: ammonium fluoride: citric acid: urea: 3-aminopropyltriethoxysilane = (5-8): (1.5-2.5): (0.5-1): (2-4): 1.
[0008] Furthermore, the preparation method of the aminoCo3O4 includes the following steps: I. Weigh 5-8 parts of cobalt nitrate hexahydrate and 2-4 parts of urea and add them to 70 parts of deionized water. Stir at 500 r / min for 30 min. Weigh 1.5-2.5 parts of ammonium fluoride and add them to the mixture. Sonicate at 30 kHz for 20 min. Continue stirring at the above speed for 20 min to obtain the hydrothermal stock solution. II. The hydrothermal stock solution obtained in step I was subjected to hydrothermal treatment at 150℃ for 12 hours, and was washed alternately with deionized water and anhydrous ethanol 3 times each, and dried at 65℃ for 24 hours to obtain CoOOH. III. Add 0.5-1 part of citric acid to the CoOOH obtained in step II and grind for 10 min. Then calcine at 400℃ for 2 h and cool naturally to room temperature to obtain Co3O4. IV. Weigh 1 part of 3-aminopropyltriethoxysilane and add it to 30 parts of a composite alcohol solution, wherein the composite alcohol solution is composed of materials in the following mass ratio: deionized water: anhydrous ethanol = 3:7. Stir at 500 r / min for 30 min. Add the Co3O4 obtained in step III and stir at the above stirring speed for 30 min. Then, perform hydrothermal treatment at 120℃ for 12 h. Wash with deionized water and anhydrous ethanol alternately 3 times each. Dry at 65℃ for 24 h to obtain aminoCo3O4.
[0009] This invention also provides a method for preparing an inorganic modified composite gel material, comprising the following steps: Step 1: Weigh 9-15 parts of acrylic acid and 3 parts of glycerol and add them to 50 parts of deionized water. Stir at 500 r / min for 30 min. Weigh 9-15 parts of potassium hydroxide and add them to the mixture. Continue stirring at the same speed for 30 min to obtain the pre-reaction solution. Step 2: Weigh 0.5 parts of MABAA and add it to the pre-reaction liquid obtained in Step 1. Stir at a speed of 500 r / min for 30 min to obtain the crosslinking liquid. Step 3: Weigh 2 parts of aminoCo3O4 and 0.5 parts of ammonium persulfate and add them to the crosslinking solution obtained in Step 2. Stir at 500 r / min for 30 min, then heat at 90℃ for 2 h. Weigh 0.5-1.2 parts of ammonium bicarbonate and add them to the solution. Stir evenly, pour into a mold, and shape to obtain the gel material.
[0010] Compared with the prior art, the present invention has the following beneficial effects: This invention introduces residual carboxyl groups onto the surface of Co3O4 through citric acid-assisted calcination. Utilizing the pre-adsorption regulation of Co sites by these carboxyl groups, selective grafting of APTES is guided to construct a molecular-level carboxyl-amino proximity interface. This interface reduces the electron density at Co sites through the electron-withdrawing effect of the carboxyl groups, weakening the adsorption strength of CO intermediates. Simultaneously, the amino group acts as a proton donor, shortening the proton transfer distance, thus synergistically optimizing the PCET kinetics of CO2 reduction and significantly improving CO selectivity and reaction rate.
[0011] This invention uses PAA as a gel backbone, utilizing the -COO of PAA. - The PAA forms a coordination crosslink with the Co sites on the Co3O4 surface, while the remaining -COOH groups of the PAA form hydrogen bonds with the amino groups on the catalyst surface to assist in crosslinking, thus constructing a coordination-hydrogen bond synergistic crosslinking network. This network not only achieves stable anchoring of the catalyst, but also constructs low-barrier proton channels through the carboxyl-amino acid base pair effect, forming a highly efficient gas-liquid-solid three-phase interface, realizing the interfacial enrichment and efficient conversion of CO2. Attached Figure Description
[0012] Figure 1 The image shows a physical representation of the inorganic modified composite gel material proposed in this application. Figure 2 The graphs show the adsorption energies of the inorganic modified composite gel materials prepared in the examples and comparative examples. Figure 3 CO product testing of inorganic modified composite gel materials prepared for examples and comparative examples in gas-liquid and gas-liquid-solid phases; Figure 4 The CO product test of the inorganic modified composite gel material prepared in Example 2 under different pH conditions.
[0013] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the embodiments of the invention to explain the invention and do not constitute a limitation thereof. Detailed Implementation
[0014] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.
[0015] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.
[0016] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values (including integers and fractions) within those ranges.
[0017] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”
[0018] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.
[0019] This invention provides an inorganic modified composite gel material and its preparation method.
[0020] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0021] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.
[0022] The preparation method and characterization in the following examples are based on... Figures 1-4 Unless otherwise specified, all methods are conventional. Unless otherwise specified, all parts of the materials used in the following examples are by weight, and all raw materials are new materials purchased from the market. The composite alcohol solution is composed of materials in the following mass ratio: deionized water: anhydrous ethanol = 3:7.
[0023] Example 1: An inorganic modified composite gel material comprises the following materials in parts by weight: 2 parts aminoCo3O4, 0.5 parts NH4HCO3, 3 parts glycerol, 9 parts acrylic acid, 9 parts potassium hydroxide, 0.5 parts MBAA, 0.5 parts ammonium persulfate, and 50 parts deionized water.
[0024] The preparation method of aminoCo3O4 is as follows: I. Weigh 5 parts of cobalt nitrate hexahydrate and 2 parts of urea and add them to 70 parts of deionized water. Stir at 500 r / min for 30 min. Weigh 1.5 parts of ammonium fluoride and add them to the mixture. Sonicate at 30 kHz for 20 min. Continue stirring at the above speed for 20 min to obtain the hydrothermal stock solution. II. The hydrothermal stock solution obtained in step I was subjected to hydrothermal treatment at 150℃ for 12 hours, and was washed alternately with deionized water and anhydrous ethanol 3 times each, and dried at 65℃ for 24 hours to obtain CoOOH. III. Add 0.5 parts of citric acid to the CoOOH obtained in step II and grind for 10 min. Then calcine at 400℃ for 2 h and cool naturally to room temperature to obtain Co3O4. IV. Weigh 1 part of 3-aminopropyltriethoxysilane and add it to 30 parts of the composite alcohol solution. Stir at 500 r / min for 30 min. Add the Co3O4 obtained in step III and stir at the same speed for 30 min. Then, perform hydrothermal treatment at 120℃ for 12 h. Wash the mixture alternately with deionized water and anhydrous ethanol 3 times each. Dry the mixture at 65℃ for 24 h to obtain aminoCo3O4.
[0025] This embodiment also provides a method for preparing an inorganic modified composite gel material, the steps of which are as follows: Step 1: Weigh 9 parts of acrylic acid and 3 parts of glycerol and add them to 50 parts of deionized water. Stir at 500 r / min for 30 min. Weigh 9 parts of potassium hydroxide and add them to the mixture. Continue stirring at the same speed for 30 min to obtain the pre-reaction solution. Step 2: Weigh 0.5 parts of MABAA and add it to the pre-reaction liquid obtained in Step 1. Stir at a speed of 500 r / min for 30 min to obtain the crosslinking liquid. Step 3: Weigh 2 parts of aminoCo3O4 and 0.5 parts of ammonium persulfate and add them to the crosslinking solution obtained in Step 2. Stir at 500 r / min for 30 min, then heat at 90℃ for 2 h. Weigh 0.5 parts of ammonium bicarbonate and add it to the solution. Stir evenly, pour into a mold, and shape to obtain the gel material.
[0026] Example 2: An inorganic modified composite gel material comprises the following materials in parts by weight: 2 parts aminoCo3O4, 0.9 parts NH4HCO3, 3 parts glycerol, 12 parts acrylic acid, 12 parts potassium hydroxide, 0.5 parts MBAA, 0.5 parts ammonium persulfate, and 50 parts deionized water.
[0027] The preparation method of aminoCo3O4 is as follows: I. Weigh 6.5 parts of cobalt nitrate hexahydrate and 3 parts of urea and add them to 70 parts of deionized water. Stir at 500 r / min for 30 min. Weigh 2 parts of ammonium fluoride and add them to the mixture. Sonicate at 30 kHz for 20 min. Continue stirring at the above speed for 20 min to obtain the hydrothermal stock solution. II. The hydrothermal stock solution obtained in step I was subjected to hydrothermal treatment at 150℃ for 12 hours, and was washed alternately with deionized water and anhydrous ethanol 3 times each, and dried at 65℃ for 24 hours to obtain CoOOH. III. Add 0.8 parts of citric acid to the CoOOH obtained in step II and grind for 10 min. Then calcine at 400℃ for 2 h and cool naturally to room temperature to obtain Co3O4. IV. Weigh 1 part of 3-aminopropyltriethoxysilane and add it to 30 parts of the composite alcohol solution. Stir at 500 r / min for 30 min. Add the Co3O4 obtained in step III and stir at the same speed for 30 min. Then, perform hydrothermal treatment at 120℃ for 12 h. Wash the mixture alternately with deionized water and anhydrous ethanol 3 times each. Dry the mixture at 65℃ for 24 h to obtain aminoCo3O4.
[0028] This embodiment also provides a method for preparing an inorganic modified composite gel material, the steps of which are as follows: Step 1: Weigh 12 parts of acrylic acid and 3 parts of glycerol and add them to 50 parts of deionized water. Stir at 500 r / min for 30 min. Weigh 12 parts of potassium hydroxide and add them to the mixture. Continue stirring at the same speed for 30 min to obtain the pre-reaction solution. Step 2: Weigh 0.5 parts of MABAA and add it to the pre-reaction liquid obtained in Step 1. Stir at a speed of 500 r / min for 30 min to obtain the crosslinking liquid. Step 3: Weigh 2 parts of aminoCo3O4 and 0.5 parts of ammonium persulfate and add them to the crosslinking solution obtained in Step 2. Stir at 500 r / min for 30 min, then heat at 90℃ for 2 h. Weigh 0.9 parts of ammonium bicarbonate and add them to the solution. Stir evenly, pour into a mold, and shape to obtain the gel material.
[0029] Example 3: An inorganic modified composite gel material, comprising the following parts by weight: 2 parts aminoCo3O4, 1.2 parts NH4HCO3, 3 parts glycerol, 15 parts acrylic acid, 15 parts potassium hydroxide, 0.5 parts MBAA, 0.5 parts ammonium persulfate, and 50 parts deionized water.
[0030] The preparation method of aminoCo3O4 is as follows: I. Weigh 8 parts of cobalt nitrate hexahydrate and 4 parts of urea and add them to 70 parts of deionized water. Stir at 500 r / min for 30 min. Weigh 2.5 parts of ammonium fluoride and add them to the mixture. Sonicate at 30 kHz for 20 min. Continue stirring at the above speed for 20 min to obtain the hydrothermal stock solution. II. The hydrothermal stock solution obtained in step I was subjected to hydrothermal treatment at 150℃ for 12 hours, and was washed alternately with deionized water and anhydrous ethanol 3 times each, and dried at 65℃ for 24 hours to obtain CoOOH. III. Add 1 part of citric acid to the CoOOH obtained in step II and grind for 10 min. Then calcine at 400℃ for 2 h and cool naturally to room temperature to obtain Co3O4. IV. Weigh 1 part of 3-aminopropyltriethoxysilane and add it to 30 parts of the composite alcohol solution. Stir at 500 r / min for 30 min. Add the Co3O4 obtained in step III and stir at the same speed for 30 min. Then, perform hydrothermal treatment at 120℃ for 12 h. Wash the mixture alternately with deionized water and anhydrous ethanol 3 times each. Dry the mixture at 65℃ for 24 h to obtain aminoCo3O4.
[0031] This embodiment also provides a method for preparing an inorganic modified composite gel material, the steps of which are as follows: Step 1: Weigh 15 parts of acrylic acid and 3 parts of glycerol and add them to 50 parts of deionized water. Stir at 500 r / min for 30 min. Weigh 15 parts of potassium hydroxide and add them to the mixture. Continue stirring at the same speed for 30 min to obtain the pre-reaction solution. Step 2: Weigh 0.5 parts of MABAA and add it to the pre-reaction liquid obtained in Step 1. Stir at a speed of 500 r / min for 30 min to obtain the crosslinking liquid. Step 3: Weigh 2 parts of aminoCo3O4 and 0.5 parts of ammonium persulfate and add them to the crosslinking solution obtained in Step 2. Stir at 500 r / min for 30 min, then heat at 90℃ for 2 h. Weigh 1.2 parts of ammonium bicarbonate and add them to the solution. Stir evenly, pour into a mold, and shape to obtain the gel material.
[0032] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that Co3O4 was not amination treated; the rest is the same as Example 2.
[0033] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that aminoCo3O4 was not added; the rest is the same as Example 2.
[0034] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that ammonium bicarbonate was not added; the rest is the same as Example 2.
[0035] The following tests were performed on the prepared gel material: Figure 1 The image shows the actual gel material prepared in Example 2, which can be seen to have a high overall looseness.
[0036] Figure 2 The adsorption energy test diagrams of the gel materials prepared in the examples and comparative examples show that after Co modification, the overall adsorption energy of the material gradually increases, promoting the forward reaction.
[0037] Figure 3 The CO product tests of the gel materials prepared for the examples and comparative examples under gas-liquid and gas-liquid-solid phases show that, compared with the gel material modified with aminoCo3O4, the performance of the comparative example is significantly reduced. The electron density of the Co site is reduced by the electron-withdrawing effect of the carboxyl group, which weakens the adsorption strength of the CO intermediate. At the same time, the amino group acts as a proton donor to shorten the proton transfer distance, which synergistically optimizes the PCET kinetics of CO2 reduction and significantly improves the CO selectivity and reaction rate.
[0038] Meanwhile, the products of CO under different pH conditions were tested, and the results are as follows: Figure 4 As shown, the amount of CO produced by the gel material prepared in Example 2 decreased only slightly at different pH levels, further demonstrating that the gel material has high pH applicability.
[0039] This invention belongs to the field of gel material synthesis technology, specifically referring to an inorganic modified composite gel material and its preparation method, comprising the following materials in parts by weight: 2 parts aminoCo3O4, 0.5-1.2 parts NH4HCO3, 3 parts glycerol, 9-15 parts acrylic acid, 9-15 parts potassium hydroxide, 0.5 parts MBAA, and 0.5 parts ammonium persulfate. This material uses CoOOH to prepare carboxyl-modified porous Co3O4, and then uses APTES amino grafting to construct a coordination microenvironment to optimize CO2 reduction. A gel is formed through coordination-hydrogen bonding crosslinking with polyacrylic acid, constructing a proton and three-phase interface to enhance catalytic performance, and exhibiting pH-responsive reversible regeneration capability.
[0040] Obviously, the above comparative examples and embodiments are only a part of the comparative examples and embodiments of the present invention, and they, along with the comparative examples and embodiments referenced based on such examples, are all within the scope of protection of this invention.
[0041] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
[0042] The present invention and its embodiments have been described above. This description is not restrictive, and the accompanying drawings are only one embodiment of the present invention. The actual application is not limited to this. In conclusion, if those skilled in the art are inspired by this description and design similar methods and embodiments without departing from the spirit of the present invention, they should all fall within the protection scope of the present invention.
Claims
1. A composite gel material based on inorganic modification, characterized in that, The material comprises the following parts by weight: 2 parts aminoCo3O4, 0.5-1.2 parts NH4HCO3, 3 parts glycerol, 9-15 parts acrylic acid, 9-15 parts potassium hydroxide, 0.5 parts N,N'-methylenebisacrylamide, 0.5 parts ammonium persulfate, and 50 parts deionized water; The aminoCo3O4 comprises materials in the following mass ratio: cobalt nitrate hexahydrate: ammonium fluoride: citric acid: urea: 3-aminopropyltriethoxysilane = (5-8): (1.5-2.5): (0.5-1): (2-4):
1.
2. The inorganic modified composite gel material according to claim 1, characterized in that, The preparation method of the aminoCo3O4 includes the following steps: Cobalt nitrate hexahydrate and urea were added to water, stirred, and then ammonium fluoride was added and sonicated to obtain the hydrothermal stock solution. The hydrothermal stock solution was subjected to a first hydrothermal treatment, washed, and dried to obtain CoOOH. Add citric acid to CoOOH, grind, and calcine to obtain Co3O4; 3-Aminopropyltriethoxysilane was added to the composite alcohol solution and stirred. Then Co3O4 was added and stirred again. A second hydrothermal treatment was performed, followed by washing and drying to obtain aminoCo3O4.
3. The inorganic modified composite gel material according to claim 2, characterized in that, The first hydrothermal treatment was performed at a temperature of 150°C for 12 hours.
4. The inorganic modified composite gel material according to claim 2, characterized in that, The second hydrothermal treatment was performed at a temperature of 120°C for 12 hours.
5. The inorganic modified composite gel material according to claim 2, characterized in that, The calcination temperature was 400℃ and the time was 2 hours.
6. The inorganic-modified composite gel material according to claim 2, characterized in that, The composite alcohol solution is composed of materials in the following mass ratio: deionized water: anhydrous ethanol = 3:
7.
7. The inorganic-modified composite gel material according to claim 2, characterized in that, The mass ratio of cobalt nitrate hexahydrate, urea, and water is (5-8):(2-4):
70.
8. The inorganic modified composite gel material according to claim 2, characterized in that, The mass ratio of 3-aminopropyltriethoxysilane to the composite alcohol solution is 1:
30.
9. A method for preparing an inorganic modified composite gel material according to any one of claims 1 to 8, characterized in that, Includes the following steps: Acrylic acid and glycerol were added to deionized water and stirred. Then potassium hydroxide was added and stirred to obtain the solution before the reaction. N,N'-methylenebisacrylamide was added to the solution before the reaction and stirred to obtain a crosslinking solution; Amino Co3O4 and ammonium persulfate were added to the crosslinking solution, stirred, heated, and then ammonium bicarbonate was added. The mixture was placed in a mold and shaped to obtain a gel material.
10. The method for preparing an inorganic modified composite gel material according to claim 9, characterized in that, The heating temperature is 90℃ and the time is 2 hours.